Stabilized fabric softening compositions

ABSTRACT

A fabric care composition comprises a polyamine functional polymer and a crystal growth inhibitor selected from the group consisting of carboxylic compounds, organic mono and diphosphonic acids, and salts and complexes thereof, and mixture thereof. In one embodiment, the polyamine functional polymer has a molecular weight between 200 and 10,000 and, when the crystal growth inhibitor is selected from carboxylic acid, organic diphosphonic acid, and mixtures thereof, the crystal growth inhibitor is present in an amount of less than 1% by weight of the composition. In another embodiment, the crystal growth inhibitor is present in an amount of from 0.005 to 0.2 percent by weight of the composition.

FIELD OF THE INVENTION

The present invention relates to a fabric care composition comprising apolyamino-functional polymer, whereby effective stabilisation of thecomposition is obtained.

BACKGROUND OF THE INVENTION

The appearance of colored fabrics, e.g., clothing, bedding, householdfabrics such table linens is one of the areas of concern for consumers.Indeed, upon typical consumer's uses of the fabrics such as wearing,washing, rinsing and/or tumble-drying of fabrics, a loss in the fabricappearance; which is at least partly due to loss of color fidelity andcolor definition, can take place. Such a problem of color loss is evenmore acute after multiwash cycles.

It is therefore an object of the invention to provide a compositionwhich provides improved color care to the laundered fabrics, especiallyafter multiwash cycles.

Recently, a new class of materials, namely, the amino-functionalpolymers, have found increasing use in the treatment of fabrics in orderto provide care to the color of fabrics.

However, it has now been found that compositions comprising theseamino-functional polymers tend to lead to storage stability problem.This problem can be characterised by a yellowing of the composition aswell as resulting malodours on the treated fabrics. This problem is evenmore acute when the product is formulated as a stand-alone product.Indeed, when fully-formulated such as in a softening composition, theperfume present within provides a certain malodour coverage thusrendering the resulting malodour more acceptable. In constrast, forstand alone product, perfume, unless present at very high level, do notsufficiently cover the malodour. High levels of perfume, however,increases the formulation cost. Furthermore, high levels of perfume tocover the malodour still does not provide a long-lasting malodourcoverage. Indeed, the perfume will provide instant malodour coverage butupon storage the perfume which contain volatile top-notes will evaporatethus lessening the malodour coverage benefit.

Accordingly, the formulator of a fabric care composition is faced withthe dual problem of formulating a composition which provides care to thefabrics without being detrimental to the stability of the composition.

The Applicant has now surprisingly found that the provision of a crystalgrowth inhibitor to compositions comprising modified amino-functionalpolymer overcomes the problem.

DETAILED DESCRIPTION OF THE INVENTION

Amino-functional Polymer

An essential component of the invention is an amino-functional polymer.The amino-functional polymer advantageously provides care to the colorsof fabrics.

The amino-functional polymers of the present invention are water-solubleor dispersible, polyamines. Typically, the amino-functional polymers foruse herein have a molecular weight between 200 and 10⁶, preferablybetween 600 and 20,000, most preferably between 1000 and 10,000. Thesepolyamines comprise backbones that can be either linear or cyclic. Thepolyamine backbones can also comprise polyamine branching chains to agreater or lesser degree. Preferably, the polyamine backbones describedherein are modified in such a manner that at least one, preferably eachnitrogen of the polyamine chain is thereafter described in terms of aunit that is substituted, quaternized, oxidized, or combinationsthereof.

For the purposes of the present invention the term “modification” as itrelates to the chemical structure of the polyamines is defined asreplacing a backbone —NH hydrogen atom by an R′ unit (substitution),quaternizing a backbone nitrogen (quaternized) or oxidizing a backbonenitrogen to the N-oxide (oxidized). The terms “modification” and“substitution” are used interchangeably when referring to the process ofreplacing a hydrogen atom attached to a backbone nitrogen with an R′unit. Quaternization or oxidation may take place in some circumstanceswithout substitution, but substitution is preferably accompanied byoxidation or quaternization of at least one backbone nitrogen.

The linear or non-cyclic polyamine backbones that comprise theamino-functional polymer have the general formula:

The cyclic polyamine backbones that comprise the amino-functionalpolymer have the general formula:

The above backbones prior to optional but preferred subsequentmodification, comprise primary, secondary and tertiary amine nitrogensconnected by R “linking” units.

For the purpose of the present invention, primary amine nitrogenscomprising the backbone or branching chain once modified are defined asV or Z “terminal” units. For example, when a primary amine moiety,located at the end of the main polyamine backbone or branching chainhaving the structure:

H₂N—[R]—

is modified according to the present invention, it is thereafter definedas a V “terminal” unit, or simply a V unit. However, for the purposes ofthe present invention, some or all of the primary amine moieties canremain unmodified subject to the restrictions further described hereinbelow. These unmodified primary amine moieties by virtue of theirposition in the backbone chain remain “terminal” units. Likewise, when aprimary amine moiety, located at the end of the main polyamine backbonehaving the structure:

—NH₂

is modified according to the present invention, it is thereafter definedas a Z “terminal” unit, or simply a Z unit. This unit can remainunmodified subject to the restrictions further described herein below.

In a similar manner, secondary amine nitrogens comprising the backboneor branching chain once modified are defined as W “backbone” units. Forexample, when a secondary amine moiety, the major constituent of thebackbones and branching chains of the present invention, having thestructure:

is modified according to the present invention, it is thereafter definedas a W “backbone” unit, or simply a W unit. However, for the purposes ofthe present invention, some or all of the secondary amine moieties canremain unmodified. These unmodified secondary amine moieties by virtueof their position in the backbone chain remain “backbone” units.

In a further similar manner, tertiary amine nitrogens comprising thebackbone or branching chain once modified are further referred to as Y“branching” units. For example, when a tertiary amine moiety, which is achain branch point of either the polyamine backbone or other branchingchains or rings, having the structure:

is modified according to the present invention, it is thereafter definedas a Y “branching” unit, or simply a Y unit. However, for the purposesof the present invention, some or all or the tertiary amine moieties canremain unmodified. These unmodified tertiary amine moieties by virtue oftheir position in the backbone chain remain “branching” units. The Runits associated with the V, W and Y unit nitrogens which serve toconnect the polyamine nitrogens, are described herein below.

The final modified structure of the polyamines of the present inventioncan be therefore represented by the general formula:

V_((n+1))W_(m)Y_(n)Z

for linear amino-functional polymer and by the general formula:

V_((n−k+1))W_(m)Y_(n)Y′_(k)Z

for cyclic aminofunctional polymer. For the case of polyaminescomprising rings, a Y′ unit of the formula:

serves as a branch point for a backbone or branch ring. For every Y′unit there is a Y unit having the formula:

that will form the connection point of the ring to the main polymerchain or branch. In the unique case where the backbone is a completering, the polyamine backbone has the formula:

therefore comprising no Z terminal unit and having the formula:

V_(n−k)W_(m)Y_(n)Y′_(k)

wherein k is the number of ring forming branching units. Preferably thepolyamine backbones of the present invention comprise no rings.

In the case of non-cyclic polyamines, the ratio of the index n to theindex m relates to the relative degree of branching. A fullynon-branched linear modified polyamine according to the presentinvention has the formula:

VW_(m)Z

that is, n is equal to 0. The greater the value of n (the lower theratio of m to n), the greater the degree of branching in the molecule.Typically the value for m ranges from a minimum value of 2 to 700,preferably 4 to 400, however larger values of m, especially when thevalue of the index n is very low or nearly 0, are also preferred.

Each polyamine nitrogen whether primary, secondary or tertiary, oncemodified according to the present invention, is further defined as beinga member of one of three general classes; simple substituted,quaternized or oxidized. Those polyamine nitrogen units not modified areclassed into V, W, Y, Y′ or Z units depending on whether they areprimary, secondary or tertiary nitrogens. That is unmodified primaryamine nitrogens are V or Z units, unmodified secondary amine nitrogensare W units or Y′ units and unmodified tertiary amine nitrogens are Yunits for the purposes of the present invention.

Modified primary amine moieties are defined as V “terminal” units havingone of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

 wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Modified secondary amine moieties are defined as W “backbone” unitshaving one of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

 wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Other modified secondary amine moieties are defined as Y′ units havingone of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

 wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Modified tertiary amine moieties are defined as Y “branching” unitshaving one of three forms:

a) unmodified units having the structure:

b) quaternized units having the structure:

 wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Certain modified primary amine moieties are defined as Z “terminal”units having one of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

 wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

When any position on a nitrogen is unsubstituted of unmodified, it isunderstood that hydrogen will substitute for R′. For example, a primaryamine unit comprising one R′ unit in the form of a hydroxyethyl moietyis a V terminal unit having the formula (HOCH₂CH₂)HN—.

For the purposes of the present invention there are two types of chainterminating units, the V and Z units. The Z “terminal” unit derives froma terminal primary amino moiety of the structure —NH₂. Non-cyclicpolyamine backbones according to the present invention comprise only oneZ unit whereas cyclic polyamines can comprise no Z units. The Z“terminal” unit can be substituted with any of the R′ units describedfurther herein below, except when the Z unit is modified to form anN-oxide. In the case where the Z unit nitrogen is oxidized to anN-oxide, the nitrogen must be modified and therefore R′ cannot be ahydrogen.

The polyamines of the present invention comprise backbone R “linking”units that serve to connect the nitrogen atoms of the backbone. R unitscomprise units that for the purposes of the present invention arereferred to as “hydrocarbyl R” units and “oxy R” units. The“hydrocarbyl” R units are C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃-C₁₂hydroxyalkylene wherein the hydroxyl moiety may take any position on theR unit chain except the carbon atoms directly connected to the polyaminebackbone nitrogens; C₄-C₁₂ dihydroxyalkylene wherein the hydroxylmoieties may occupy any two of the carbon atoms of the R unit chainexcept those carbon atoms directly connected to the polyamine backbonenitrogens; C₈-C₁₂ dialkylarylene which for the purpose of the presentinvention are arylene moieties having two alkyl substituent groups aspart of the linking chain. For example, a dialkylarylene unit has theformula:

although the unit need not be 1,4-substituted, but can also be 1,2 or1,3 substituted C₂-C₁₂ alkylene, preferably ethylene, 1,2-propylene, andmixtures thereof, more preferably ethylene. The “oxy” R units comprise—(R¹O)_(x)R⁵(OR¹)_(x)—,—CH₂CH(OR²)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH(OR²)CH₂)_(w)—, —CH₂CH(OR²)CH₂—,—(R¹O)_(x)R¹—, and mixtures thereof. Preferred R units are selected fromthe group consisting of C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂dihydroxyalkylene, C₈-C₁₂ dialkylarylene, —(R¹O)_(x)R¹—,—CH₂CH(OR²)CH₂—, —(CH₂CH(OH)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH—(OH)CH₂)_(w)—,—(R¹O)_(x)R⁵(OR¹)_(x)—, more preferred R units are C₂-C₁₂ alkylene,C₃-C₁₂ hydroxy-alkylene, C₄-C₁₂ dihydroxyalkylene, —(R¹O)_(x)R¹—,—(R¹O)_(x)R⁵(OR¹)_(x)—,—(CH₂CH(OH)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH—(OH)CH₂)_(w)—, and mixturesthereof, even more preferred R units are C₂-C₁₂ alkylene, C₃hydroxyalkylene, and mixtures thereof, most preferred are C₂-C₆alkylene. The most preferred backbones of the present invention compriseat least 50% R units that are ethylene.

R¹ units are C₂-C₆ alkylene, and mixtures thereof, preferably ethylene.

R² is hydrogen, and —(R¹O)_(x)B, preferably hydrogen.

R³ is C₁-C₁₈ alkyl, C₇-C₁₂ arylalkylene, C₇-C₁₂ alkyl substituted aryl,C₆-C₁₂ aryl, and mixtures thereof, preferably C₁-C₁₂ alkyl, C₇-C₁₂arylalkylene, more preferably C₁-C₁₂ alkyl, most preferably methyl. R³units serve as part of R′ units described herein below.

R⁴ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene, C₆-C₁₀arylene, preferably C₁-C₁₂ alkylene, C₈-C₁₂ arylalkylene, morepreferably C₂-C₈ alkylene, most preferably ethylene or butylene.

R⁵ is C₁-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene,C₈-C₁₂ dialkylarylene, —C(O)—, —C(O)NHR⁶NHC(O)—, —C(O)(R⁴)_(r)C(O)—,—R¹(OR¹)—, —CH₂CH(OH)CH₂O(R¹O)_(y)R¹OCH₂CH(OH)CH₂—, —C(O)(R⁴)_(r)C(O)—,—CH₂CH(OH)CH₂—, R⁵ is preferably ethylene, —C(O)—, —C(O)NHR⁶NHC(O)—,—R¹(OR¹)—, —CH₂CH(OH)CH₂—, —CH₂CH(OH)CH₂O(R¹O)_(y)R¹OCH₂CH—(OH)CH₂—,more preferably —CH₂CH(OH)CH₂—.

R⁶ is C₂-C₁₂ alkylene or C₆-C₁₂ arylene.

The preferred “oxy” R units are further defined in terms of the R¹, R²,and R⁵ units. Preferred “oxy” R units comprise the preferred R¹, R², andR⁵ units. The preferred cotton soil release agents of the presentinvention comprise at least 50% R¹ units that are ethylene. PreferredR¹, R², and R⁵ units are combined with the “oxy” R units to yield thepreferred “oxy” R units in the following manner.

i) Substituting more preferred R⁵ into —(CH₂CH₂O)_(x)R⁵(OCH₂CH₂)_(x)—yields —(CH₂CH₂O)_(x)CH₂CHOHCH₂(OCH₂CH₂)_(x)—.

ii) Substituting preferred R¹ and R² into—(CH₂CH(OR²)CH₂O)_(z)—(R¹O)_(y)R¹O(CH₂CH(OR²)CH₂)_(w)— yields—(CH₂CH(OH)CH₂O)_(z—(CH) ₂CH₂O)_(y)CH₂CH₂O(CH₂CH(OH)CH₂)_(w)—.

iii) Substituting preferred R² into —CH₂CH(OR²)CH₂— yields—CH₂CH(OH)CH₂—.

R′ units are selected from the group consisting of hydrogen, C₁-C₂₂alkyl, C₃-C₂₂ alkenyl, C₇-C₂₂ arylalkyl, C₂-C₂₂ hydroxyalkyl,—(CH₂)_(p)CO₂M, —(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M, —(CH₂)_(p)PO₃M,—(R¹O)_(m)B, —C(O)R³, preferably hydrogen, C₂-C₂₂ hydroxyalkylene,benzyl, C₁-C₂₂ alkylene, —(R¹O)_(m)B, —C(O)R³, —(CH₂)_(p)CO₂M,—(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M, more preferably C₁-C₂₂ alkylene,—(R₁O)_(x)B, —C(O)R³, —(CH₂)_(p)CO₂M, —(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M,most preferably C₁-C₂₂ alkylene, —(R¹O)_(x)B, and —C(O)R³. When nomodification or substitution is made on a nitrogen then hydrogen atomwill remain as the moiety representing R′. A most preferred R′ unit is(R¹O)_(x)B.

R′ units do not comprise hydrogen atom when the V, W or Z units areoxidized, that is the nitrogens are N-oxides. For example, the backbonechain or branching chains do not comprise units of the followingstructure:

Additionally, R′ units do not comprise carbonyl moieties directly bondedto a nitrogen atom when the V, W or Z units are oxidized, that is, thenitrogens are N-oxides. According to the present invention, the R′ unit—C(O)R³ moiety is not bonded to an N-oxide modified nitrogen, that is,there are no N-oxide amides having the structure

or combinations thereof.

B is hydrogen, C₁-C₆ alkyl, —(CH₂)_(q)SO₃M, —(CH₂)_(p)CO₂M,—(CH₂)_(q)—(CHSO₃M)CH₂SO₃M, —(CH₂)_(q)(CHSO₂M)CH₂SO₃M, —(CH₂)_(p)PO₃M,—PO₃M, preferably hydrogen, —(CH₂)_(q)SO₃M, —(CH₂)_(q)(CHSO₃M)CH₂SO₃M,—(CH₂)_(q)—(CHSO₂M)CH₂SO₃M, more preferably hydrogen or —(CH₂)_(q)SO₃M.

M is hydrogen or a water soluble cation in sufficient amount to satisfycharge balance. For example, a sodium cation equally satisfies—(CH₂)_(p)CO₂M, and —(CH₂)_(q)SO₃M, thereby resulting in—(CH₂)_(p)CO₂Na, and —(CH₂)_(q)SO₃Na moieties. More than one monovalentcation, (sodium, potassium, etc.) can be combined to satisfy therequired chemical charge balance. However, more than one anionic groupmay be charge balanced by a divalent cation, or more than onemono-valent cation may be necessary to satisfy the charge requirementsof a poly-anionic radical. For example, a —(CH₂)_(p)PO₃M moietysubstituted with sodium atoms has the formula —(CH₂)_(p)PO₃Na₃. Divalentcations such as calcium (Ca²⁺) or magnesium (Mg²⁺) may be substitutedfor or combined with other suitable mono-valent water soluble cations.Preferred cations are sodium and potassium, more preferred is sodium.

X is a water soluble anion such as chlorine (Cl⁻), bromine (Br⁻) andiodine (I⁻) or X can be any negatively charged radical such as sulfate(SO₄ ²⁻) and methosulfate (CH₃SO₃ ⁻).

The formula indices have the following values: p has the value from 1 to6, q has the value from 0 to 6; r has the value 0 or 1; w has the value0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; zhas the value 0 or 1; m has the value from 2 to 700, preferably from 4to 400, n has the

value from 0 to 350, preferably from 0 to 200; m+n has the value of atleast 5.

Preferably x has a value lying in the range of from 1 to 20, preferablyfrom 1 to 10.

The preferred amino-functional polymers of the present inventioncomprise polyamine backbones wherein less than 50% of the R groupscomprise “oxy” R units, preferably less than 20% , more preferably lessthan 5%, most preferably the R units comprise no “oxy” R units.

The most preferred amino-functional polymers which comprise no “oxy” Runits comprise polyamine backbones wherein less than 50% of the R groupscomprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene,and 1,3-propylene comprise 3 or less carbon atoms and are the preferred“hydrocarbyl” R units. That is when backbone R units are C₂-C₁₂alkylene, preferred is C₂-C₃ alkylene, most preferred is ethylene.

The amino-functional polymers of the present invention comprise modifiedhomogeneous and non-homogeneous polyamine backbones, wherein 100% orless of the —NH units are modified. For the purpose of the presentinvention the term “homogeneous polyamine backbone” is defined as apolyamine backbone having R units that are the same (i.e., allethylene). However, this sameness definition does not exclude polyaminesthat comprise other extraneous units comprising the polymer backbonewhich are present due to an artifact of the chosen method of chemicalsynthesis. For example, it is known to those skilled in the art thatethanolamine may be used as an “initiator” in the synthesis ofpolyethyleneimines, therefore a sample of polyethyleneimine thatcomprises one hydroxyethyl moiety resulting from the polymerization“initiator” would be considered to comprise a homogeneous polyaminebackbone for the purposes of the present invention. A polyamine backbonecomprising all ethylene R units wherein no branching Y units are presentis a homogeneous backbone. A polyamine backbone comprising all ethyleneR units is a homogeneous backbone regardless of the degree of branchingor the number of cyclic branches present.

For the purposes of the present invention the term “non-homogeneouspolymer backbone” refers to polyamine backbones that are a composite ofvarious R unit lengths and R unit types. For example, a non-homogeneousbackbone comprises R units that are a mixture of ethylene and1,2-propylene units. For the purposes of the present invention a mixtureof “hydrocarbyl” and “oxy” R units is not necessary to provide anon-homogeneous backbone.

Preferred amino-functional polymers of the present invention comprisehomogeneous polyamine backbones that are totally or partiallysubstituted by polyethyleneoxy moieties, totally or partiallyquaternized amines, nitrogens totally or partially oxidized to N-oxides,and mixtures thereof. However, not all backbone amine nitrogens must bemodified in the same manner, the choice of modification being left tothe specific needs of the formulator. The degree of ethoxylation is alsodetermined by the specific requirements of the formulator.

The preferred polyamines that comprise the backbone of the compounds ofthe present invention are generally polyalkyleneimines (PAI's),preferably polyethyleneimines (PEI's), or PEI's connected by moietieshaving longer R units than the parent PAI's or PEI's.

Preferred amine polymer backbones comprise R units that are C₂ alkylene(ethylene) units, also known as polyethylenimines (PEI's). PreferredPEI's have at least moderate branching, that is the ratio of m to n isless than 4:1, however PEI's having a ratio of m to n of 2:1 are mostpreferred. Preferred backbones, prior to modification have the generalformula:

wherein R′, m and n are the same as defined herein above. PreferredPEI's will have a molecular weight greater than 200 daltons.

The relative proportions of primary, secondary and tertiary amine unitsin the polyamine backbone, especially in the case of PEI's, will vary,depending on the manner of preparation. Each hydrogen atom attached toeach nitrogen atom of the polyamine backbone chain represents apotential site for subsequent substitution, quaternization or oxidation.

These polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al.,issued Dec, 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16,1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S.Pat. No. 2,553,696, Wilson, issued May 21, 1951; all herein incorporatedby reference.

Examples of amino-functional polymers comprising PEI's, are illustratedin Formulas I-IV:

Formula I depicts an amino-functional polymer comprising a PEI backbonewherein all substitutable nitrogens are modified by replacement ofhydrogen with a polyoxyalkyleneoxy unit, —(CH₂CH₂O)H, having the formula

This is an example of an amino-functional polymer that is fully modifiedby one type of moiety.

Formula II depicts an amino-functional polymer comprising a PEI backbonewherein all substitutable primary amine nitrogens are modified byreplacement of hydrogen with a polyoxyalkyleneoxy unit, —(CH₂CH₂O)₂H,the molecule is then modified by subsequent oxidation of all oxidizableprimary and secondary nitrogens to N-oxides, said polymer having theformula

Formula III depicts an amino-functional polymer comprising a PEIbackbone wherein all backbone hydrogen atoms are substituted and somebackbone amine units are quaternized. The substituents arepolyoxyalkyleneoxy units, —(CH₂CH₂O)₇H, or methyl groups. The modifiedPEI has the formula

Formula IV depicts an amino-functional polymer comprising a PEI backbonewherein the backbone nitrogens are modified by substitution (i.e. by—(CH₂CH₂O)₃H or methyl), quaternized, oxidized to N-oxides orcombinations thereof. The resulting polymer has the formula

In the above examples, not all nitrogens of a unit class comprise thesame modification. The present invention allows the formulator to have aportion of the secondary amine nitrogens ethoxylated while having othersecondary amine nitrogens oxidized to N-oxides. This also applies to theprimary amine nitrogens, in that the formulator may choose to modify allor a portion of the primary amine nitrogens with one or moresubstituents prior to oxidation or quaternization. Any possiblecombination of R′ groups can be substituted on the primary and secondaryamine nitrogens, except for the restrictions described herein above.

Commercially available amino-functional polymer suitable for use hereinare poly(ethyleneimine) with a MW 1200, hydroxyethylatedpoly(ethyleneimine) from Polysciences, with a MW 2000, and 80%hydroxyethylated poly(ethyleneimine) from Aldrich.

A typical amount of amino-functional polymer to be employed in thecomposition of the invention is preferably up to 90% by weight,preferably from 0.01% to 50% active by weight, more preferably from 0.1%to 20% by weight and most preferably from 0.5% to 15% by weight of thecomposition.

Crystal Growth Inhibitor

A crystal growth inhibitor (CGI) is an essential component of theinvention. By “crystal growth inhibitor”, it is meant a compound thatreduces the rate of formation of inorganic microcrystals, therebyreducing the size and/or the amount of such micro-crystals at the fabricsurface.

The suitable CGI for use herein can be defined by the following testprocedure, so called crystal growth inhibition test measurement.

Crystal Growth Inhibition Test Measurement

The ability for a compound to inhibit crystal growth can be assessed byevaluating the impact in vitro on the growth rate of inorganicmicro-crystals. For this purpose, a system developed by G. H. Nancollasin 1964, described in Nancollas, G. H and Koutsoukos, P. G. “CalciumPhosphate Nucleation and Growth in solution.” Prog. Crystal GrowthCharact. 3, 77-102 (1980) can be used. This system consists of measuringthe growth rate of calcium phosphate crystals seeded with hydroxyapatite([Ca₅(PO₄)₃OH] or HAP) in the presence of CaCl₂ and NaH₂PO₄. Calciumphosphate growth liberates protons that can be titrated with a strongbase. The amount of base needed to keep the pH constant over the crystalgrowth enables persons skilled in the art to measure the crystal growthrate directly as well as to determine the effects of potential crystalgrowth rate inhibitors. A typical plot of such an experiment is givenbelow:

The observed t-lag value defines the efficiency of a compound to inhibitthe growth of calcium phosphate crystals; wherein the higher the t-lag,the better the CGI.

The following procedure can be used to build the plot given aboveexperimentally:

Place 350 mL of distilled water (distilled twice), 35 mL of KCl 2.1M, 50mL of CaCl₂ 0.0175M and 50 mL of KH₂PO₄ 0.01M in a reaction vessel.Insert a glass pH electrode and a standard calomel reference electrodeconnected to an auto-titrator. Bubble nitrogen gas and stabilize thetemperature of the reaction mixture to 37° C. When temperature and pHare stabilized, add the CGI candidate at the concentration to be tested(e.g. 1.10⁻⁶M). Titrate to pH 7.4 with KOH 0.05M. Then seed the reactionmixture with 5 mL of hydroxyapatite slurry [Ca₅(PO₄)OH].

The hydroxyapatite slurry is prepared as follows:

100 gr of Bio-Gel® HTP hydroxyapatite powder is dispersed in 1 L ofdistilled water. The pH of the resulting slurry is lowered to 2.5 bydropwise addition of HCl 6N. This is then heated to boiling and refluxedwhile stirring for seven days in a 2 L round-bottom flask connected to acondenser. After cooling, to room temperature, pH is adjusted to 12.0 bydropwise addition of 50% NaOH and the slurry is refluxed for anotherseven days as before. The slurry is allowed to settle for to days andthe supernatant is suctioned off. The flask is refilled with 1.5 L ofdistilled water, stirred vigorously, an allowed to settle again for twodays. A total of seven rinses as described above are performed. The pHis adjusted to 7.0 by dropwise addition of HCl 2N while stirringvigorously. The resulting slurry is stored at 37° C. for eleven months.

The plot shown above is obtained by recording the amount of base addedover time to maintain the pH of the reaction medium. T-lag for aparticular crystal growth inhibitor is determined graphically asdescribed in the figure above.

The crystal growth inhibitors to be used for the purpose of thisinvention have a t-lag of at least 10 minutes at a concentration of1.10⁻⁶M, preferably at least 20 minutes, most preferably at least 50minutes.

Still another suitable method for determining the crystal growthinhibition property of the selected component which is comparable to theT-lag method is by a visual grading. The method is as follows:

A multicycle laundry test is performed over several (e.g. 10) cycles ofrepeated washing and tumble drying. The conditions used arerepresentative for the desired geographical region (e.g. domesticwashing machine used, detergent used, rinse added product use, waterhardness, clothing articles washed etc.). At least two test legs are runin parallel, including the composition of the invention and a separatereference leg. After the required number of washing cycles have beenperformed the test garments (articles of clothing) are taken forcomparison by expert graders under controlled lighting conditions. Thevisual grading is a better/worse comparison of the visible crystallineresidue on the surface of the test garments, comparing the test leg tothe reference leg. Dark coloured, knitted cotton articles are mostsuitable for this comparison.

In addition, the crystal growth inhibitors, differentiate themselvesfrom the chelating agents by their low binding affinity for copperdefined by its Log K, i.e the ML/M.L Log K at 25 C., 0.1 ionic strength,of the CGI is of less than 15, preferably less than 12.

Preferably, the CGI for use in the present invention are selected fromcarboxylic compounds, organic monophosphonic acids, organic diphosphonicacids, and mixtures thereof.

Carboxylic Compounds

Typical of carboxylic compound for use herein are the carboxyliccompounds selected from glycolic acid, phytic acid, monomericpolycarboxylic acids, homo or copolymeric polycarboxylic acids or theirsalts in which the polycarboxylic acid comprises at least two carboxylicradicals separated from each other by not more than two carbon atoms.

When utilised in salt form, alkali metals, such as sodium, potassium andlithium, or alkanolammonium salts are preferred.

Organic detergent CGIs suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “polycarboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate CGI can generally be added to thecomposition in acid form, but can also be added in the form of aneutralised salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate CGIs are a variety of categories ofuseful materials. One important category of polycarboxylate CGIsencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in U.S. Pat. Nos. 3,128,287 and 3,635,830. See also “TMS/TDS”CGIs of U.S. Pat. No. 4,663,071. Suitable ether polycarboxylates alsoinclude cyclic compounds, particularly alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other useful CGI include the ether hydroxypolycarboxylates, polyacrylatepolymers, copolymers of maleic anhydride with ethylene or vinyl methylether, or acrylic acid, 1,3,5-trihydroxy benzene-2,4,6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

The molecular weight for these polymers and copolymers is preferablybelow 100,000, most preferably between 500 and 50,000.

Commercially available polymers, suitable for use herein, which preventthe precipitation of the salts of the buffering component upon dilutionof the composition in water are the polyacrylate polymers sold under thetradename Good-Rite® from BF Goodrich, Acrysol® from Rohm & Haas,Sokalan® from BASF, Norasol® from Norso Haas. Preferred commerciallyavailable polymers are the polyacrylate polymers, especially theNorasol® polyacrylate polymers and more preferred are the polyacrylatepolymer Norasol® 410N (MW 10,000) and the polyacrylate polymer modifiedwith aminophosphonic groups Norasol® 440N (MW 4000) and itscorresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.Citrates, e.g., citric acid and soluble salts thereof (particularlysodium salt), are polycarboxylate CGI suitable for use herein.

Also suitable in the compositions containing the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984. Useful succinic acid CGI includethe C₅-C₂₀ alkyl and alkenyl succinic acids and salts thereof. Aparticularly preferred compound of this type is dodecenylsuccinic acid.Specific examples of succinate CGIs include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Laurylsuccinates are thepreferred CGIs of this group, and are described in EP 0,200,263.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226and in U.S. Pat. No. 3,308,067. See also U.S. Pat. No. 3,723,322.

Organic Monophosphonic Acid

Organo monophosphonic acid or one of its salts or complexes is alsosuitable for use herein as a CGI.

By organo monophosphonic acid it is meant herein an organomonophosphonic acid which does not contain nitrogen as part of itschemical structure. This definition therefore excludes the organoaminophosphonates, which however may be included in compositions of theinvention as heavy metal ion sequestrants.

The organo monophosphonic acid component may be present in its acid formor in the form of one of its salts or complexes with a suitable countercation. Preferably any salts/complexes are water soluble, with thealkali metal and alkaline earth metal salts/complexes being especiallypreferred.

A prefered organo monophosphonic acid is2-phosphonobutane-1,2,4-tricarboxylic acid commercially available fromBayer under the tradename of Bayhibit.

Organodiphosphonic Acid

Organo diphosphonic acid or one of its salts or complexes is alsosuitable for use herein as a CGI.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrants.

The organo diphosphonic acid component may be present in its acid formor in the form of one of its salts or complexes with a suitable countercation. Preferably any salts/complexes are water soluble, with thealkali metal and alkaline earth metal salts/complexes being especiallypreferred.

The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid andmore preferably a C₂ diphosphonic acid selected from ethylenediphosphonic acid, α-hydroxy-2 phenyl ethyl diphosphonic acid, methylenediphosphonic acid, vinylidene 1,1 diphosphonic acid, 1,2 dihydroxyethane1,1 diphosphonic acid and hydroxy-ethane 1,1 diphosphonic acid and anysalts thereof and mixtures thereof.

A most preferred organo diphosphonic acid is hydroxy-ethane 1,1diphosphonic acid (HEDP).

Among the above described classes of CGI, preferred classes for useherein are the class of organic monophosphonic acids and/or organicdiphosphonic acids.

For the purpose of the invention, when the CGI is selected fromcarboxylic acid, organic diphosphonic acid, and mixtures thereof, theCGI is present at a level of less than 1%, preferably from 0.005% to0.5%, more preferably from 0.05% to 0.50%, most preferably from 0.1% to0.2% by weight of the composition.

Typical levels for CGI components other than carboxylic acid, organicdiphosphonic acid, and mixtures thereof, like organo monophosphonicacid, are in amount of less than 10%, more preferably from 0.005% to0.50%, most preferably from 0.1% to 0.2% by weight of the composition.

Preferably for the purpose of the invention, stabilisation of thepolyamino-functional polymer containing composition are best stabilisedwhere a weight ratio of said CGI to said polymer is of from 0.005:1 to0.5:1, preferably from 0.01:1 to 0.1:1 is present.

The composition of the invention can be employed in stand alone productincluding pre- or post-wash additives. It can also be employed. It canalso be used in fully-formulated compositions including laundrycompositions as well as rinse added fabric softener compositions anddryer added compositions (e.g. sheets) which provide softening and/orantistatic benefits, and rinse added compositions.

The composition may comprises optional ingredients such as a dye fixingagent, a fabric softener compound and further optional ingredient.

Dye Fixing Agent

The composition of the invention may optionally comprise a dye fixingagent. Dye fixing agents, or “fixatives”, are well-known, commerciallyavailable materials which are designed to improve the appearance of dyedfabrics by minimizing the loss of dye from fabrics due to washing. Notincluded within this definition are components which are fabricsofteners or those described hereinbefore as amino-functional polymers,

Many dye fixing agents are cationic, and are based on variousquaternized or otherwise cationically charged organic nitrogencompounds. Cationic fixatives are available under various trade namesfrom several suppliers. Representative examples include: CROSCOLOR PMF(July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No.8544) from Crosfield; INDOSOL E-50 (Feb. 27, 1984, Ref. No. 6008.35.84;polyethyleneamine-based) from Sandoz; SANDOFIX TPS, which is alsoavailable from Sandoz and is a preferred polycationic fixative for useherein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWINSRF-O and REWIN DWR from CHT-Beitlich GMBH, Tinofix® ECO, Tinofix® FRDand Solfin® available from Ciba-Geigy.

Other cationic dye fixing agents are described in “Aftertreatments forimproving the fastness of dyes on textile fibres” by Christopher C. Cook(REV. PROG. COLORATION Vol. 12, 1982). Dye fixing agents suitable foruse in the present invention are ammonium compounds such as fattyacid—diamine condensates e.g. the hydrochloride, acetate, metosulphateand benzyl hydrochloride of oleyidiethyl aminoethylamide,oleylmethyl-diethylenediaminemethosulphate, monostearyl-ethylenediaminotrimethylammonium methosulphate and oxidized products of tertiaryamines; derivatives of polymeric alkyldiamines, polyamine-cyanuricchloride condensates and aminated glycerol dichlorohydrins.

A typical amount of the dye fixing agent to be employed in thecomposition of the invention is preferably up 90% by weight, preferablyup to 50% by weight, more preferably from 0.001% to 10% by weight, mostpreferably from 0.5% to 5% active by weight of the composition.

The composition of the invention may also be formulated as a fabricsoftening composition. Accordingly, when formulated as a softeningcomposition, it will comprises a fabric softening compound.

Fabric Softening Compound

Typical levels of incorporation of the softening compound in thesoftening composition are of from 1% to 80% by weight, preferably from5% to 75%, more preferably from 15% to 70%, and even more preferablyfrom 19% to 65%, by weight of the composition.

The fabric softener compound is preferably selected from a cationic,nonionic, amphoteric or anionic fabric softening component. Typical ofthe cationic softening components are the quaternary ammonium compoundsor amine precursors thereof as defined hereinafter.

A)—Quaternary Ammonium Fabric Softening Active Compound

(1) Preferred quaternary ammonium fabric softening active compound havethe formula

or the formula:

wherein Q is a carbonyl unit having the formula:

each R unit is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,and mixtures thereof, preferably methyl or hydroxy alkyl; each R¹ unitis independently linear or branched C₁₁-C₂₂ alkyl, linear or branchedC₁₁-C₂₂ alkenyl, and mixtures thereof, R² is hydrogen, C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, and mixtures thereof; X is an anion which iscompatible with fabric softener actives and adjunct ingredients; theindex m is from 1 to 4, preferably 2; the index n is from 1 to 4,preferably 2.

An example of a preferred fabric softener active is a mixture ofquaternized amines having the formula:

wherein R is preferably methyl; R¹ is a linear or branched alkyl oralkenyl chain comprising at least 11 atoms, preferably at least 15atoms. In the above fabric softener example, the unit —O₂CR¹ representsa fatty acyl unit which is typically derived from a triglyceride source.The triglyceride source is preferably derived from tallow, partiallyhydrogenated tallow, lard, partially hydrogenated lard, vegetable oilsand/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, etc. and mixtures of these oils.

The preferred fabric softening actives of the present invention are theDiester and/or Diamide Quaternary Ammonium (DEQA) compounds, thediesters and diamides having the formula:

wherein R, R¹, X, and n are the same as defined herein above forformulas (1) and (2), and Q has the formula:

These preferred fabric softening actives are formed from the reaction ofan amine with a fatty acyl unit to form an amine intermediate having theformula:

wherein R is preferably methyl, Q and R¹ are as defined herein before;followed by quaternization to the final softener active.

Non-limiting examples of preferred amines which are used to form theDEQA fabric softening actives according to the present invention includemethyl bis(2-hydroxyethyl)amine having the formula:

methyl bis(2-hydroxypropyl)amine having the formula:

methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:

methyl bis(2-aminoethyl)amine having the formula:

triethanol amine having the formula:

di(2-aminoethyl) ethanolamine having the formula:

The counterion, X⁽⁻⁾ above, can be any softener-compatible anion,preferably the anion of a strong acid, for example, chloride, bromide,methylsulfate, ethylsulfate, sulfate, nitrate and the like, morepreferably chloride or methyl sulfate. The anion can also, but lesspreferably, carry a double charge in which case X⁽⁻⁾ represents half agroup.

Tallow and canola oil are convenient and inexpensive sources of fattyacyl units which are suitable for use in the present invention as R¹units. The following are non-limiting examples of quaternary ammoniumcompounds suitable for use in the compositions of the present invention.The term “tallowyl” as used herein below indicates the R¹ unit isderived from a tallow triglyceride source and is a mixture of fatty acylunits. Likewise, the use of the term canolyl refers to a mixture offatty acyl units derived from canola oil.

TABLE II

Fabric Softener Actives

N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(tallowyl-oxy-ethyl)-N-methyl,N-(2-hydroxyethyl) ammoniumchloride;

N,N-di(canolyl-oxy-ethyl)-N-methyl,N-(2-hydroxyethyl) ammonium chloride;

N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride

N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammoniumchloride;

N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammoniumchloride;

N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;

N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;

N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammoniumchloride;

N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;

1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and

1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;

and mixtures of the above actives.

Other examples of quaternay ammoniun softening compounds aremethylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate andmethylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammoniummethylsulfate; these materials are available from Witco Chemical Companyunder the trade names Varisoft® 222 and Varisoft® 110, respectively.

Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethylammonium chloride, where the tallow chains are at least partiallyunsaturated.

The level of unsaturation contained within the tallow, canola, or otherfatty acyl unit chain can be measured by the Iodine Value (IV) of thecorresponding fatty acid, which in the present case should preferably bein the range of from 5 to 100 with two categories of compounds beingdistinguished, having a IV below or above 25.

Indeed, for compounds having the formula:

derived from tallow fatty acids, when the Iodine Value is from 5 to 25,preferably 15 to 20, it has been found that a cis/trans isomer weightratio greater than about 30/70, preferably greater than about 50/50 andmore preferably greater than about 70/30 provides optimalconcentrability. For compounds of this type made from tallow fatty acidshaving a Iodine Value of above 25, the ratio of cis to trans isomers hasbeen found to be less critical unless very high concentrations areneeded.

Other suitable examples of fabric softener actives are derived fromfatty acyl groups wherein the terms “tallowyl” and “canolyl” in theabove examples are replaced by the terms “cocoyl, palmyl, lauryl, oleyl,ricinoleyl, stearyl, palmityl,” which correspond to the triglyceridesource from which the fatty acyl units are derived. These alternativefatty acyl sources can comprise either fully saturated, or preferably atleast partly unsaturated chains.

As described herein before, R units are preferably methyl, however,suitable fabric softener actives are described by replacing the term“methyl” in the above examples in Table II with the units “ethyl,ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl”.

The counter ion, X, in the examples of Table II can be suitably replacedby bromide, methylsulfate, formate, sulfate, nitrate, and mixturesthereof. In fact, the anion, X, is merely present as a counterion of thepositively charged quaternary ammonium compounds. The scope of thisinvention is not considered limited to any particular anion.

For the preceding ester fabric softening agents, the pH of thecompositions herein is an important parameter of the present invention.Indeed, it influences the stability of the quaternary ammonium or amineprecursors compounds, especially in prolonged storage conditions.

The pH, as defined in the present context, is measured in the neatcompositions at 20° C. While these compositions are operable at pH ofless than about 6.0, for optimum hydrolytic stability of thesecompositions, the neat pH, measured in the above-mentioned conditions,must preferably be in the range of from about 2.0 to about 5, preferablyin the range of 2.5 to 4.5, preferably about 2.5 to about 3.5. The pH ofthese compositions herein can be regulated by the addition of a Bronstedacid.

Examples of suitable acids include the inorganic mineral acids,carboxylic acids, in particular the low molecular weight (C₁-C₅)carboxylic acids, and alkylsulfonic acids. Suitable inorganic acidsinclude HCl, H₂SO₄, HNO₃ and H₃PO₄. Suitable organic acids includeformic, acetic, citric, methylsulfonic and ethylsulfonic acid. Preferredacids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid,and benzoic acids.

As used herein, when the diester is specified, it will include themonoester that is normally present in manufacture. For softening, underno/low detergent carry-over laundry conditions the percentage ofmonoester should be as low as possible, preferably no more than about2.5%. However, under high detergent carry-over conditions, somemonoester is preferred.

The overall ratios of diester to monoester are from about 100:1 to about2:1, preferably from about 50:1 to about 5:1, more preferably from about13:1 to about 8:1. Under high detergent carry-over conditions, thedi/monoester ratio is preferably about 11:1. The level of monoesterpresent can be controlled in the manufacturing of the softener compound.

Mixtures of actives of formula (1) and (2) may also be prepared.

2)—Still other suitable quaternary ammonium fabric softening compoundsfor use herein are cationic nitrogenous salts having two or more longchain acyclic aliphatic C₈-C₂₂ hydrocarbon groups or one said group andan arylalkyl group which can be used either alone or as part of amixture are selected from the group consisting of:

(i) acyclic quaternary ammonium salts having the formula:

 wherein R⁴ is an acyclic aliphatic C₈-C₂₂ hydrocarbon group, R⁵ is aC₁-C₄ saturated alkyl or hydroxyalkyl group, R⁸ is selected from thegroup consisting of R⁴ and R⁵ groups, and A⁻ is an anion defined asabove;

(ii) diamino alkoxylated quaternary ammonium salts having the formula:

 wherein n is equal to 1 to about 5, and R¹, R², R⁵ and A⁻ are asdefined above;

(iii) mixtures thereof.

Examples of the above class cationic nitrogenous salts are thewell-known dialkyldi methylammonium salts such asditallowdimethylammonium chloride, ditallowdimethylammoniummethylsulfate, di(hydrogenatedtallow)dimethylammonium chloride,distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.Di(hydrogenatedtallow)di methylammonium chloride andditallowdimethylammonium chloride are preferred. Examples ofcommercially available dialkyldimethyl ammonium salts usable in thepresent invention are di(hydrogenatedtallow)dimethylammonium chloride(trade name Adogen® 442), ditallowdimethylammonium chloride (trade nameAdogen® 470, Praepagen® 3445), distearyl dimethylammonium chloride(trade name Arosurf® TA-100), all available from Witco Chemical Company.Dibehenyldimethylammonium chloride is sold under the trade name KemamineQ-2802C by Humko Chemical Division of Witco Chemical Corporation.

Dimethylstearylbenzyl ammonium chloride is sold under the trade namesVarisoft® SDC by Witco Chemical Company and Ammonyx® 490 by OnyxChemical Company.

B)—Amine Fabric Softening Active Compound

Suitable amine fabric softening compounds for use herein, which may bein amine form or cationic form are selected from:

(i)—Reaction products of higher fatty acids with a polyamine selectedfrom the group consisting of hydroxyalkylalkylenediamines anddialkylenetriamines and mixtures thereof. These reaction products aremixtures of several compounds in view of the multi-functional structureof the polyamines.

The preferred Component (i) is a nitrogenous compound selected from thegroup consisting of the reaction product mixtures or some selectedcomponents of the mixtures.

One preferred component (i) is a compound selected from the groupconsisting of substituted imidazoline compounds having the formula:

wherein R⁷ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group and R⁸ is adivalent C₁-C₃ alkylene group.

Component (i) materials are commercially available as: Mazamide® 6, soldby Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals;stearic hydroxyethyl imidazoline sold under the trade names of Alkazine®ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals,Inc.; N,N″-ditallowalkoyldiethylenetriamine;1-tallowamidoethyl-2-tallowimidazoline (wherein in the precedingstructure R¹ is an aliphatic C₁₅-C₁₇ hydrocarbon group and R⁸ is adivalent ethylene group).

Certain of the Components (i) can also be first dispersed in a Bronstedacid dispersing aid having a pKa value of not greater than about 4;provided that the pH of the final composition is not greater than about6. Some preferred dispersing aids are hydrochloric acid, phosphoricacid, or methylsulfonic acid.

Both N,N″-ditallowalkoyldiethylenetriamine and1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallowfatty acids and diethylenetriamine, and are precursors of the cationicfabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazoliniummethylsulfate (see “Cationic Surface Active Agents as Fabric Softeners,”R. R. Egan, Journal of the American Oil Chemicals' Society, January1978, pages 118-121). N,N″-ditallow alkoyidiethylenetriamine and1-tallowamidoethyl-2-tallowimidazoline can be obtained from WitcoChemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold byWitco Chemical Company under the tradename Varisoft® 475.

(ii)—softener having the formula:

wherein each R² is a C₁₋₆ alkylene group, preferably an ethylene group;and G is an oxygen atom or an —NR— group; and each R, R¹, R² and R⁵ havethe definitions given above and A⁻ has the definitions given above forX⁻.

An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazoliniumchloride wherein R¹ is an acyclic aliphatic C₁₅-C₁₇ hydrocarbon group,R² is an ethylene group, G is a NH group, R⁵ is a methyl group and A⁻ isa chloride anion.

(iii)—softener having the formula:

wherein R, R¹, R², and A⁻ are defined as above.

An example of Compound (iii) is the compound having the formula:

wherein R¹ is derived from oleic acid.

Additional fabric softening agents useful herein are described in U.S.Pat. No. 4,661,269, issued Apr. 28, 1987, in the names of Toan Trinh,Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat.No. 4,439,335, Burns, issued Mar. 27, 1984; and in U.S. Pat. No.3,861,870, Edwards and Diehl; U.S. Pat. No. 4,308,151, Cambre; U.S. Pat.No. 3,886,075, Bernardino; U.S. Pat. No. 4,233,164, Davis; U.S. Pat. No.4,401,578, Verbruggen; U.S. Pat. No. 3,974,076, Wiersema and Rieke; U.S.Pat. No. 4,237,016, Rudkin, Clint, and Young; and European PatentApplication publication No. 472,178, by Yamamura et al., all of saiddocuments being incorporated herein by reference.

Of course, the term “softening active” can also encompass mixedsoftening active agents.

Preferred among the classes of softener compounds disclosed hereinbefore are the diester or diamido quaternary ammonium fabric softeningactive compound (DEQA).

Fully formulated fabric softening compositions may contain, in additionto the hereinbefore described components, one or more of the followingingredients.

Optional Ingredients

(A) Liquid Carrier

Another optional, but preferred, ingredient is a liquid carrier. Theliquid carrier employed in the instant compositions is preferably atleast primarily water due to its low cost, relative availability,safety, and environmental compatibility. The level of water in theliquid carrier is preferably at least about 50%, most preferably atleast about 60%, by weight of the carrier. Mixtures of water and lowmolecular weight, e.g., <about 200, organic solvent, e.g., loweralcohols such as ethanol, propanol, isopropanol or butanol are useful asthe carrier liquid. Low molecular weight alcohols include monohydric,dihydric (glycol, etc.) trihydric (glycerol, etc.), and higherpolyhydric (polyols) alcohols.

(B)—Additional Solvents

The compositions of the present invention may comprise one or moresolvents which provide increased ease of formulation. These ease offormulation solvents are all disclosed in WO 97/03169. This isparticularly the case when formulating liquid, clear fabric softeningcompositions. When employed, the ease of formulation solvent systempreferably comprises less than about 40%, preferably from about 10% toabout 35%, more preferably from about 12% to about 25%, and even morepreferably from about 14% to about 20%, by weight of the composition.The ease of formulation solvent is selected to minimize solvent odorimpact in the composition and to provide a low viscosity to the finalcomposition. For example, isopropyl alcohol is not very effective andhas a strong odor. n-Propyl alcohol is more effective, but also has adistinct odor. Several butyl alcohols also have odors but can be usedfor effective clarity/stability, especially when used as part of a easeof formulation solvent system to minimize their odor. The alcohols arealso selected for optimum low temperature stability, that is they areable to form compositions that are liquid with acceptable lowviscosities and translucent, preferably clear, down to about 40° F.(about 4.4° C.) and are able to recover after storage down to about 20°F. (about minus 6.7° C.).

The suitability of any ease of formulation solvent for the formulationof the liquid, concentrated, preferably clear, fabric softenercompositions herein with the requisite stability is surprisinglyselective. Suitable solvents can be selected based upon theiroctanol/water partition coefficient (P) as defined in WO 97/03169.

The ease of formulation solvents herein are selected from those having aClogP of from about 0.15 to about 0.64, preferably from about 0.25 toabout 0.62, and more preferably from about 0.40 to about 0.60, said easeof formulation solvent preferably being at least somewhat asymmetric,and preferably having a melting, or solidification, point that allows itto be liquid at, or near room temperature. Solvents that have a lowmolecular weight and are biodegradable are also desirable for somepurposes. The more assymetric solvents appear to be very desirable,whereas the highly symmetrical solvents such as 1,7-heptanediol, or1,4-bis(hydroxymethyl)cyclohexane, which have a center of symmetry,appear to be unable to provide the essential clear compositions whenused alone, even though their ClogP values fall in the preferred range.

The most preferred ease of formulation solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

Operable ease of formulation solvents are disclosed and listed belowwhich have ClogP values which fall within the requisite range. Theseinclude mono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. Particularly preferred ease of formulation solventsinclude hexanediols such as 1,2-Hexanediol and 2-Ethyl-1,3-hexanedioland pentanediols such as 2,2,4-Trimethyl-1,3-pentanediol.

(C)—Dispersibility Aids

Relatively concentrated compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixturesthereof. These aids are described in WO 94/20597, specifically on page14, line 12 to page 20, line 12, which is herein incorporated byreference.

When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (I), e.g., the mono-long chain alkyl cationic surfactantand/or the fatty acid which are reactants used to form the biodegradablefabric softener active as discussed hereinbefore, or added as a separatecomponent. The total level of dispersibility aid includes any amountthat may be present as part of component (I).

Inorganic viscosity/dispersibility control agents which can also actlike or augment the effect of the surfactant concentration aids, includewater-soluble, ionizable salts which can also optionally be incorporatedinto the compositions of the present invention. A wide variety ofionizable salts can be used. Examples of suitable salts are the halidesof the Group IA and IIA metals of the Periodic Table of the Elements,e.g., calcium chloride, magnesium chloride, sodium chloride, potassiumbromide, and lithium chloride. The ionizable salts are particularlyuseful during the process of mixing the ingredients to make thecompositions herein, and later to obtain the desired viscosity. Theamount of ionizable salts used depends on the amount of activeingredients used in the compositions and can be adjusted according tothe desires of the formulator. Typical levels of salts used to controlthe composition viscosity are from about 20 to about 20,000 parts permillion (ppm), preferably from about 20 to about 11,000 ppm, by weightof the composition.

Alkylene polyammonium salts can be incorporated into the composition togive viscosity control in addition to or in place of the water-soluble,ionizable salts above. In addition, these agents can act as scavengers,forming ion pairs with anionic detergent carried over from the mainwash, in the rinse, and on the fabrics, and may improve softnessperformance. These agents may stabilize the viscosity over a broaderrange of temperature, especially at low temperatures, compared to theinorganic electrolytes.

Specific examples of alkylene polyammonium salts include I-lysinemonohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.

(D)—Stabilizers

Stabilizers can be present in the compositions of the present invention.The term “stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% toabout 2%, preferably from about 0.01% to about 0.2%, more preferablyfrom about 0.035% to about 0.1% for antioxidants, and more preferablyfrom about 0.01% to about 0.2% for reductive agents. These assure goododor stability under long term storage conditions for the compositionsand compounds stored in molten form. The use of antioxidants andreductive agent stabilizers is especially critical for low scentproducts (low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox-6; butylated hydroxytoluene, available from UOP ProcessDivision under the trade name Sustane® BHT; tertiary butylhydroquinone,Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols,Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylatedhydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chainesters (C₈-C₂₂) of gallic acid, e.g., dodecyl gallate; Irganox® 1010;Irganox® 1035; Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox®3125; and mixtures thereof; preferably Irganox® 3125, Irganox® 1425,Irganox® 3114, and mixtures thereof; more preferably Irganox® 3125alone. The chemical names and CAS numbers for some of the abovestabilizers are listed in Table II below.

TABLE II Chemical Name used in Code of Antioxidant CAS No. FederalRegulations Irganox ® 1010 6683-19-8 Tetrakis(methylene(3,5-di-tert-butyl-4 hydroxyhydrocinnamate)) methane Irganox ®1035 41484-35-9 Thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate Irganox ® 1098 23128-74-7 N,N′-Hexamethylenebis(3,5-di-tert- butyl-4- hydroxyhydrocinnamamide Irganox ® B 31570-04-41171 23128-74-7 1:1 Blend of Irganox ® 1098 and Irgafos ® 168 Irganox ®1425 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate) Irganox ® 3114 65140-91-2 Calciumbis(monoethyl(3,5-di-tert- butyl-4-hydroxybenzyl)phosphonate) Irganox ®3125 34137-09-2 3,5-Di-tert-butyl-4-hydroxy- hydrocinnamic acid triesterwith 1,3,5-tris(2-hydroxyethyl)- S-triazine-2,4,6-(1H, 3H, 5H)-trioneIrgafos ® 168 31570-04-4 Tris(2,4-di-tert-butyl-phenyl)phosphite

Examples of reductive agents include sodium borohydride, hypophosphorousacid, Irgafos® 168, and mixtures thereof.

(E)—Soil Release Agent

Soil Release agents are desirably used in fabric softening compositionsof the instant invention. Any polymeric soil release agent known tothose skilled in the art can optionally be employed in the compositionsof this invention. Polymeric soil release agents are characterized byhaving both hydrophilic segments, to hydrophilize the surface ofhydrophobic fibers, such as polyester and nylon, and hydrophobicsegments, to deposit upon hydrophobic fibers and remain adhered theretothrough completion of washing and rinsing cycles and, thus, serve as ananchor for the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

The following, all included herein by reference, describe soil releasepolymers suitable for use in the present invention. U.S. Pat. No.3,959,230 Hays, issued May 25, 1976; U.S. Pat. No. 3,893,929 Basadur,issued Jul. 8, 1975; U.S. Pat. No. 4,000,093, Nicol, et al., issued Dec.28, 1976; U.S. Pat. No. 4,702,857 Gosselink, issued Oct. 27, 1987; U.S.Pat. No. 4,968,451, Scheibel et al., issued November 6; U.S. Pat. No.4,702,857, Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730,Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580,Gosselink, issued Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado etal., issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issuedMay 16, 1995; European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824, Violland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681, Ruppert et al.;U.S. Pat. Nos. 4,240,918; 4,787,989; 4,525,524; EP 279,134 A, 1988, toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N. V., 1974 all incorporated herein by reference.

Commercially available soil release agents include the METOLOSE SM100,METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K. K., SOKALANtype of material, e.g., SOKALAN HP-22, available from BASF (Germany),ZELCON 5126 (from Dupont) and MILEASE T (from ICI).

(F)—Bactericides

Examples of bactericides used in the compositions of this inventioninclude glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diolsold by Inolex Chemicals, located in Philadelphia, Pa., under the tradename Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-oneand 2-methyl4-isothiazoline-3-one sold by Rohm and Haas Company underthe trade name Kathon 1 to 1,000 ppm by weight of the agent.

(G)—Perfume

The present invention can contain a perfume. Suitable perfumes aredisclosed in U.S. Pat. No. 5,500,138, said patent being incorporatedherein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

The range of the natural raw substances can embrace not onlyreadily-volatile, but also moderately-volatile and slightly-volatilecomponents and that of the synthetics can include representatives frompractically all classes of fragrant substances, as will be evident fromthe following illustrative compilation: natural products, such as treemoss absolute, basil oil, citrus fruit oils (such as bergamot oil,mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil,patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such asfarnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol,cinnamic alcohol, aldehydes, such as citral, Helional™,alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial™(p-tert-butyl-alpha-methyidihydrocinnamaldehyde),methyinonylacetaldehyde, ketones, such as allylionone, alpha-ionone,beta-ionone, isoraldein (isomethyl-alpha-ionone), methylionone, esters,such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate,citronellyl acetate, citronellyl ethoxolate, decyl acetate,dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethylacetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate,methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.,lactones, such as gamma-undecalactone, various components often used inperfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, andmethyl-eugenol. Likewise, any conventional fragrant acetal or ketalknown in the art can be added to the present composition as an optionalcomponent of the conventionally formulated perfume (c). Suchconventional fragrant acetals and ketals include the well-known methyland ethyl acetals and ketals, as well as acetals or ketals based onbenzaldehyde, those comprising phenylethyl moieties, or more recentlydeveloped specialties such as those described in a United States Patententitled “Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes”, see U.S.Pat. No. 5,084,440, issued Jan. 28, 1992, assigned to Givaudan Corp. Ofcourse, other recent synthetic specialties can be included in theperfume compositions for fully-formulated fabric softening compositions.These include the enol ethers of alkyl-substituted oxo-tetralins andoxo-indanes as described in U.S. Pat. No. 5,332,725, Jul. 26, 1994,assigned to Givaudan; or Schiff Bases as described in U.S. Pat. No.5,264,615, Dec. 9, 1991, assigned to Givaudan.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Perfume can be present at a level of from 0% to 10%, preferably from0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric softener compositions of the presentinvention provide improved fabric perfume deposition.

(H)—Enzyme

The compositions and processes herein can optionally employ one or moreenzymes such as lipases, proteases, cellulase, amylases and peroxidases.A preferred enzyme for use herein is a cellulase enzyme. Indeed, thistype of enzyme will further provide a color care benefit to the treatedfabric. Cellulases usable herein include both bacterial and fungaltypes, preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96/34092, WO96/34945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.Stated otherwise, the compositions herein will typically comprise from0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzymepreparation. In the particular cases where activity of the enzymepreparation can be defined otherwise such as with cellulases,corresponding activity units are preferred (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzymepreparations used for the purpose of formulating the compositions ofthis invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.

Other Optional Ingredients

The present invention can include optional components conventionallyused in textile treatment compositions, for example: brighteners,colorants; surfactants; anti-shrinkage agents; fabric crisping agents;spotting agents; germicides; fungicides; anti-oxidants such as butylatedhydroxy toluene, anti-corrosion agents, antifoam agents, and the like.

The present invention can also include other compatible ingredients,including those as disclosed in WO96/02625, WO96/21714, and WO96/21715,and dispersible polyolefin such as Velustrol® as disclosed in co-pendingapplication PCT/US 97/01644, and the like. The present invention canalso contain optional chelating agents.

The benefit provided by the use of the present invention is that thepolyamino functional polymer containing composition is stabilised bymeans of the CGI. Accordingly, in an aspect of the invention, there isprovided the use of a crystal growth inhibitor to stabilise compositionscomprising amino-functional polymer.

As a consequence, the compositions of the invention provide better careto the fabrics compared to compositions which do not have suchstabilisation means. Accordingly, in another aspect of the invention,there is provided a method for providing care to the color fabrics whichcomprises the steps of contacting the fabrics with a composition of theinvention.

The color care benefit may either be assessed visually or bydetermination of the so-called delta-E values.

When the visual assessment is used, a panel of expert graders visuallycompare, according to the established panel score unit (PSU) scales,fabrics treated with and without the composition according to thepresent invention. A positive PSU value indicates a better performance(PSU scale: 0=no difference, 1=I think there is a difference, 2=I knowthere is a difference, 3=I know there is a lot of difference, 4=I knowthere is a whole lot of difference).

Another method for the assessment of the color care benefit to fabricsis the determination of the so-called delta-E values. Delta E's aredefined, for instance, in ASTM D2244. Delta E is the computed colordifference as defined in ASTM D2244, i.e. the magnitude and direction ofthe difference between two psychophysical color stimuli defined bytristimulus values, or by chromaticity coordinates and luminance factor,as computed by means of a specified set of color-difference equationsdefined in the CIE 1976 CIELAB opponent-color space, the Hunteropponent-color space, the Friele-Mac Adam-Chickering color space or anyequivalent color space.

Applications

The compositions of the invention are suitable for use in any steps ofthe domestic treatment, that is as a pretreatment composition, as a washadditive as a composition suitable for use in the rinse-cycle of thelaundry cycle or applied on a dryer-sheet. Obviously, for the purpose ofthe invention, multiple applications can be made such as treating thefabric with a pre-treatment composition of the invention and alsothereafter with a composition of the invention suitable for use in therinse cycle and/or suitable for use as a dryer-sheet. The compositionsof the invention may also be in a spray, foam, or aerosol form which forexample can be suitable for use while ironing, or applied on thesurfaces of the tumble dryer.

The invention is illustrated in the following non limiting examples, inwhich all percentages are on an active weight basis unless otherwisestated.

In the examples, the abbreviated component identifications have thefollowing meanings:

DEQA: Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride DOEQA:Di-(oleyloxyethyl) dimethyl ammonium methylsulfate DTDMAC: Ditallowdimethylammonium chloride DHEQA: Di-(soft-tallowyl-oxy-ethyl)hydroxyethyl methyl ammonium methylsulfate Fatty acid: tallow fatty acidIV = 18 Electrolyte: Calcium chloride DTDMAMS: Ditallow dimethylammonium methylsulfate SDASA: 1:2 Ratio of stearyldimethylamine:triple-pressed stearic acid Glycosperse S-20: Polyethoxylatedsorbitan monostearate available from Lonza Clay: Calcium Bentonite Clay,Bentonite L, sold by Southern Clay Products TAE25: Tallow alcoholethoxylated with 25 moles of ethylene oxide per mole of alcohol PEG:Polyethylene Glycol 4000 PEI 1800 E1: Ethoxylated polyethylene imine (MW1800, at 50% active) as synthesised in Synthesis example 1 PEI 1800 E3:Ethoxylated polyethylene imine (MW 1800, at 50% active) as synthesisedas per Synthesis example 1 PEI 1800 E7 AO: Amine oxide of ethoxylatedpolyethylene imine (MW 1800, at 50% active) as synthesised as perSynthesis example 4 PEI 1200 E1: Ethoxylated polyethylene imine (MW1200, at 50% active in water) as synthesised in Synthesis example 5 PEI1200 E2: Ethoxylated polyethylene imine (MW 1200, at 50% active inwater) as synthesised per Synthesis example 5 PEI 1200 E4: Ethoxylatedpolyethylene imine (MW 1200, at 50% active in water) as synthesised perSynthesis example 5 PEI 1200 E7: Ethoxylated polyethylene imine (MW1200, at 50% active in water) as synthesised per Synthesis example 5 PEI1200 E7 AO: Amine oxide of ethoxylated polyethylene imine (MW 1200, at50% active) as synthesised as per Synthesis example 5 and 4 Dye Fix 1:Cationic dye fixing agent (50% active) available under the tradenameTinofix Eco from Ciba-Geigy Dye Fix 2: Emulsified cationic dye fixative(30% active) available under the tradename Rewin SRF-O from CHT-BeitlichNH4Cl: Ammonium chloride LAS: Sodium linear C₁₂ alkyl benzene sulphonateTAS: Sodium tallow alcohol sulphate C25AS: Sodium C₁₂-C₁₅ linear alkylsulphate CxyEzS: Sodium C_(1x)-C_(1y) branched alkyl sulphate condensedwith z moles of ethylene oxide C45E7: A C₁₄₋₁₅ predominantly linearprimary alcohol condensed with an average of 7 moles of ethylene oxideC25 E3: A C₁₂₋₁₅ branched primary alcohol condensed with an average of 3moles of ethylene oxide Cationic Mixture of C₁₂/C₁₄ choline ester ester:Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture oftallow and a coconut oils. TFAA: C₁₆-C₁₈ alkyl N-methyl glucamide TPKFA:C12-C14 topped whole cut fatty acids Zeolite A: Hydrated SodiumAluminosilicate of formula Na₁₂(A10₂SiO₂)₁₂. 27H₂O having a primaryparticle size in the range from 0.1 to 10 micrometers Citric acid:Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with aparticle size between 200 μm and 900 μm Silicate: Amorphous SodiumSilicate (SiO₂:Na₂O; 2.0 ratio) Sulphate: Anhydrous sodium sulphateCitrate: Tri-sodium citrate dihydrate of activity 86.4% with a particlesize distribution between 425 μm and 850 μm MA/AA: Copolymer of 1:4maleic/acrylic acid, average molecular weight about 70,000. CMC: Sodiumcarboxymethyl cellulose Savinase: Proteolytic enzyme of activity 4KNPU/gCarezyme: Cellulytic enzyme of activity 1000 CEVU/g Termamyl: Amylolyticenzyme of activity 60KNU/g Lipolase: Lipolytic enzyme of activity100kLU/g all sold by NOVO Industries A/S and of activity mentioned aboveunless otherwise specified PB4: Sodium perborate tetrahydrate of nominalformula NaBO₂.3H₂O.H₂O₂ PB1: Anhydrous sodium perborate bleach ofnominal formula NaBO₂.H₂O₂ TAED: Tetraacetyl ethylene diamine DTPMP:Diethylene triamine penta (methylene phosphonate), marketed by Monsantounder the Trade name Dequest 2060 Photoactivated: Sulphonated ZincPhthalocyanin encapsulated in bleach dextrin soluble polymer Brightener:Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino)stilbene-2:2′-disulphonate. Silicone antifoam: Polydimethyldiloxane foamcontroller with Siloxane-oxyalkylene copolymer as dispersing agent witha ratio of said foam controller to said dispersing agent of 10:1 to100:1. HEDP: 1,1-hydroxyethane diphosphonic acid PBT:2-phosphonobutane-1,2,4-tricarboxylic acid Polycarboxylic:Polycarboxylic compound marketed by BASF under the tradename Sokalan CP10 Glycolic: Glycolic acid

Synthesis Example 1 Preparation of PEI 1800 E₁

Step A)—The ethoxylation is conducted in a 2 gallon stirred stainlesssteel autoclave equipped for temperature measurement and control,pressure measurement, vacuum and inert gas purging, sampling, and forintroduction of ethylene oxide as a liquid. A ˜20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid bya pump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, EpominSP-018 having a listed average molecular weight of 1800 equating to0.417 moles of polymer and 17.4 moles of nitrogen functions) is added tothe autoclave. The autoclave is then sealed and purged of air (byapplying vacuum to minus 28″ Hg followed by pressurization with nitrogento 250 psia, then venting to atmospheric pressure). The autoclavecontents are heated to 130° C. while applying vacuum. After about onehour, the autoclave is charged with nitrogen to about 250 psia whilecooling the autoclave to about 105° C. Ethylene oxide is then added tothe autoclave incrementally over time while closely monitoring theautoclave pressure, temperature, and ethylene oxide flow rate. Theethylene oxide pump is turned off and cooling is applied to limit anytemperature increase resulting from any reaction exotherm. Thetemperature is maintained between 100 and 110° C. while the totalpressure is allowed to gradually increase during the course of thereaction. After a total of 750 grams of ethylene oxide has been chargedto the autoclave (roughly equivalent to one mole ethylene oxide per PEInitrogen function), the temperature is increased to 110° C. and theautoclave is allowed to stir for an additional hour. At this point,vacuum is applied to remove any residual unreacted ethylene oxide.

Step B)—The reaction mixture is then deodorized by passing about 100 cu.ft. of inert gas (argon or nitrogen) through a gas dispersion frit andthrough the reaction mixture while agitating and heating the mixture to130° C.

The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen.

In other preparations the neutralization and deodorization isaccomplished in the reactor before discharging the product.

If a PEI 1800 E₇ is desired, the following step of catalyst additionwill be included between Step A and B.

Vacuum is continuously applied while the autoclave is cooled to about50° C. while introducing 376 g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PEInitrogen functions). The methoxide solution is sucked into the autoclaveunder vacuum and then the autoclave temperature controller setpoint isincreased to 130° C. A device is used to monitor the power consumed bythe agitator. The agitator power is monitored along with the temperatureand pressure. Agitator power and temperature values gradually increaseas methanol is removed from the autoclave and the viscosity of themixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed. The mixture is further heated andagitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles).

Other preferred examples such as PEI 1800 E2, PEI 1800 E3, PEI 1800 E15and PEI 1800 E20 can be prepared by the above method by adjusting thereaction time and the relative amount of ethylene oxide used in thereaction.

Synthesis Example 2 4.7% Quaternization of PEI 1800 E7

To a 500 ml erlenmeyer flask equipped with a magnetic stirring bar isadded poly(ethyleneimine), MW 1800 ethoxylated to a degree of 7 (224 g,0.637 mol nitrogen, prepared as in Synthesis Example 1) and acetonitrile(Baker, 150 g, 3.65 mol). Dimethyl sulfate (Aldrich, 3.8 g, 0.030 mol)is added all at once to the rapidly stirring solution, which is thenstoppered and stirred at room temperature overnight. The acetonitrile isevaporated on the rotary evaporator at ˜60° C., followed by a Kugelrohrapparatus (Aldrich) at ˜80° C. to afford ˜220 g of the desired materialas a dark brown viscous liquid. A ¹³C-NMR (D₂O) spectrum shows theabsence of a peak at ˜58 ppm corresponding to dimethyl sulfate. A ¹H-NMR(D₂O) spectrum shows the partial shifting of the peak at 2.5 ppm(methylenes attached to unquaternized nitrogens) to ˜3.0 ppm.

Synthesis Example 3 Oxidation of 4.7% Quaternized PEI 1800 E7

To a 500 ml erlenmeyer flask equipped with a magnetic stirring bar isadded poly(ethyleneimine), MW 1800 which has been ethoxylated to adegree of 7, and ˜4.7% quaternized with dimethyl sulfate (121.7 g, ˜0.32mol oxidizeable nitrogen, prepared as in Synthesis Example 2), hydrogenperoxide (Aldrich, 40 g of a 50 wt % solution in water, 0.588 mol), andwater (109.4 g). The flask is stoppered, and after an initial exothermthe solution is stirred at room temperature overnight. A ¹H-NMR (D₂O)spectrum shows the total shifting of the methylene peaks at 2.5-3.0 ppmto ˜3.5 ppm. To the solution is added ˜5 g of 0.5% Pd on aluminapellets, and the solution is allowed to stand at room temperature for ˜3days. Peroxide indicator paper shows that no peroxide is left in thesystem. The material is stored as a 46.5% solution in water.

Synthesis Example 4 Formation of Amine Oxide of PEI 1800 E₇

To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar isadded polyethyleneimine having a molecular weight of 1800 andethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800,E₇) (209 g, 0.595 mol nitrogen, prepared as in Synthesis Example I), andhydrogen peroxide (120 g of a 30 wt % solution in water, 1.06 mol). Theflask is stoppered, and after an initial exotherm the solution isstirred at room temperature overnight. ¹H-NMR (D₂O) spectrum obtained ona sample of the reaction mixture indicates complete conversion. Theresonances ascribed to methylene protons adjacent to unoxidizednitrogens have shifted from the original position at ˜2.5 ppm to ˜3.5ppm. To the reaction solution is added approximately 5 g of 0.5% Pd onalumina pellets, and the solution is allowed to stand at roomtemperature for approximately 3 days. The solution is tested and foundto be negative for peroxide by indicator paper. The material as obtainedis suitably stored as a 51.1% active solution in water.

Synthesis Example 5 Preparation of PEI 1200 E₁

Step A)—The ethoxylation is conducted in a 2 gallon stirred stainlesssteel autoclave equipped for temperature measurement and control,pressure measurement, vacuum and inert gas purging, sampling, and forintroduction of ethylene oxide as a liquid. A ˜20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid bya pump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) (having a listed averagemolecular weight of 1200 equating to about 0.625 moles of polymer and17.4 moles of nitrogen functions) is added to the autoclave. Theautoclave is then sealed and purged of air (by applying vacuum to minus28″ Hg followed by pressurization with nitrogen to 250 psia, thenventing to atmospheric pressure). The autoclave contents are heated to130° C. while applying vacuum. After about one hour, the autoclave ischarged with nitrogen to about 250 psia while cooling the autoclave toabout 105° C.

Ethylene oxide is then added to the autoclave incrementally over timewhile closely monitoring the autoclave pressure, temperature, andethylene oxide flow rate. The ethylene oxide pump is turned off andcooling is applied to limit any temperature increase resulting from anyreaction exotherm. The temperature is maintained between 100 and 110° C.while the total pressure is allowed to gradually increase during thecourse of the reaction. After a total of 750 grams of ethylene oxide hasbeen charged to the autoclave (roughly equivalent to one mole ethyleneoxide per PEI nitrogen function), the temperature is increased to 110°C. and the autoclave is allowed to stir for an additional hour. At thispoint, vacuum is applied to remove any residual unreacted ethyleneoxide.

Step B)—The reaction mixture is then deodorized by passing about 100 cu.ft. of inert gas (argon or nitrogen) through a gas dispersion frit andthrough the reaction mixture while agitating and heating the mixture to130° C.

The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen.

In other preparations the neutralization and deodorization isaccomplished in the reactor before discharging the product.

If a PEI 1200 E₇ is desired, the following step of catalyst additionwill be included between Step A and B.

Vacuum is continuously applied while the autoclave is cooled to about50° C. while introducing 376 g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PEInitrogen functions). The methoxide solution is sucked into the autoclaveunder vacuum and then the autoclave temperature controller setpoint isincreased to 130° C. A device is used to monitor the power consumed bythe agitator. The agitator power is monitored along with the temperatureand pressure. Agitator power and temperature values gradually increaseas methanol is removed from the autoclave and the viscosity of themixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed. The mixture is further heated andagitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles).

Other preferred examples such as PEI 1200 E2, PEI 1200 E3, PEI 1200 E15and PEI 1200 E20 can be prepared by the above method by adjusting thereaction time and the relative amount of ethylene oxide used in thereaction.

The corresponding amine oxide of the above ethoxylated PEI can also beprepared following synthesis Example 4.

Synthesis Example 6 9.7% Quaternization of PEI 1200 E7

To a 500 ml erlenmeyer flask equipped with a magnetic stirring bar isadded poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4g, 0.707 mol nitrogen, prepared as in Synthesis Example 5) andacetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich, 8.48 g, 0.067mol) is added all at once to the rapidly stirring solution, which isthen stoppered and stirred at room temperature overnight. Theacetonitrile is evaporated on the rotary evaporator at ˜60° C., followedby a Kugelrohr apparatus (Aldrich) at ˜80° C. to afford ˜220 g of thedesired material as a dark brown viscous liquid. A ¹³C-NMR (D₂O)spectrum shows the absence of a peak at ˜58 ppm corresponding todimethyl sulfate. A ¹H-NMR (D₂O) spectrum shows the partial shifting ofthe peak at 2.5 ppm (methylenes attached to unquaternized nitrogens) to˜3.0 ppm.

Synthesis Example 7 4.7% Oxidation of 9.5% Quaternized PEI 1200 E7

To a 500 ml erlenmeyer flask equipped with a magnetic stirring bar isadded poly(ethyleneimine), MW 1200 which has been ethoxylated to adegree of 7, and ˜9.5% quaternized with dimethyl sulfate (144 g, ˜0.37mol oxidizeable nitrogen, prepared as in Example 6), hydrogen peroxide(Aldrich, 35.4 g of a 50 wt % solution in water, 0.52 mol), and water(100 g). The flask is stoppered, and after an initial exotherm thesolution is stirred at room temperature overnight. A ¹H-NMR (D₂O)spectrum shows the total shifting of the methylene peaks at 2.5-3.0 ppmto ˜3.5 ppm. To the solution is added just enough sodium bisulfite as a40% water solution to bring the residual peroxide level down to 1-5 ppm.The sodium sulfate which forms causes an aqueous phase to separate whichcontains salts, but little or no organics. The aqueous salt phase isremoved and the desired oxidized polyethyleneimine derivative isobtained and stored as a 52% solution in water.

EXAMPLE 1

The following compositions are in accordance with the present invention

Component A B C D E F G H DEQA 2.6 2.9 18.0 19.0 19.0 — — — TAE25 — 1.0— — — — — Fatty acid 0.3 — 1.0 — — — — — Hydrochloride 0.02 0.02 0.020.02 0.02 — — — acid PEG — — 0.6 0.6 0.6 — — — Perfume 1.0 1.0 1.0 1.01.0 0.1 0.1 0.1 Silicone 0.01 0.01 0.01 0.01 0.01 — — — antifoam PEI1200 E1 3 3 3 3 — 15 — 10 PEI 1200 E2 — 3 10 — Dye fix 1 — 1 1 1 — — 10— Dye fix 2 — 2 2 2 — — — — HEDP 0.2 — — 0.2 — 0.4 — 0.8 Glycolic — 0.2— — 0.5 — 0.4 — Poly- — — 0.5 — — 0.4 — — carboxylate Electrolyte — —600 600 1200 — — — (ppm) Dye (ppm) 10 10 50 50 50 — — — Water and minorsto balance to 100 Component I J K L M DEQA 2.6 19.0 — — — Fatty acid 0.3— — — — Hydrochloride acid 0.02 0.02 — — — PEG — 0.6 — — — Perfume 1.01.0 0.1 0.1 0.2 Silicone antifoam 0.01 0.01 — — — PEI 1200 E1 3 3 15 —10 PEI 1200 E4 — — — 10 — Dye fix 1 — 1 — — 2.5 Dye fix 2 — 2 — — — PBT0.2 0.2 0.4 0.8 0.5 Polycarboxylate — — 0.4 — — Electrolyte (ppm) — 600— — — Dye (ppm) 10 50 — — — Water and minors to balance to 100 ComponentN O P Q R S DTDMAC — — — 15 — — DEQA 2.6 19.0 — — 2.6 19.0 TAE25 0.3 — —— 0.3 — Fatty acid 0.3 — — — 0.3 — Hydrochloride 0.02 0.02 — 0.02 0.020.02 acid PEG — 0.6 — 0.6 — 0.6 Perfume 1.0 1.0 0.1 1.0 1.0 1.0 Siliconeantifoam 0.01 0.01 — 0.01 0.01 0.01 PEI 1800 E1 3 3 10 3 3 3 HEDP 0.20.2 — — — — PBT — — — — 0.2 0.2 Glycolic — — 0.2 — — — polycarboxylic —— — 0.2 — — Dye fix 1 1 1 10 1 1 1 Dye fix 2 2 2 — 2 2 2 Electrolyte(ppm) — 600 — 600 — 600 Dye (ppm) 10 50 — 50 10 50 Water and minors tobalance to 100

EXAMPLE 2

The following compositions for use as dryer-added sheets are inaccordance with the invention

T U V W X Y Z AA BB DOEQA 40 40 25 — — — — — — DHEQA — — — 20 20 — — — —DTDMAMS — — — — — 20 20 12 60 SDASA 30 30 30 20 20 30 30 20 —Glycosperse S-20 — — — 10 10 — — — — Glycerol — — — — — 20 20 10 —Monostearate Clay 4 4 4 3 3 4 4 4 — Perfume 0.7 0.7 1.1 0.7 0.7 1.6 1.62.6 1.4 PEI 1800 E4 — — 5 — — — — — — PEI 1200 E1 — — — 4 4 2.2 2.2 — —PEI 1800 E3 2 2 — — — — — 5 7.0 Dye fix 1 2 2 5 4 4 2.2 2.2 5 3 HEDP 0.2— — 0.5 — — — — 0.7 BPT — 0.2 — — 0.9 — 0.2 Glycolic — — 0.2 — — 0.2 — —— Polycarboxylic — — 0.2 — — — — 0.4 — Stearic acid to balance

EXAMPLE 3

The following detergent formulations, are in accordance with the presentinvention:

CC DD EE Zeolite A 24.0 23.0 23.0 Sulphate 9.0 — — MA/AA 4.0 4.0 4.0 LAS8.0 8.0 8.0 TAS — 2.0 2.0 Silicate 3.0 3.0 3.0 CMC 1.0 0.4 0.4Brightener 0.2 — — Soap 1.0 — — DTPMP 0.4 0.4 0.4 C45E7 2.5 2.0 2.0C25E3 2.5 2.0 2.0 Silicone antifoam 0.3 5.0 5.0 Perfume 0.3 0.3 0.3Carbonate 13.0 16.0 16.0 Citrate — 5.0 5.0 PB4 18.0 — — PB1 4.0 14.014.0 TAED 3.0 6.0 6.0 Photoactivated bleach 0.02% — — Savinase 1.0 1.01.0 Lipolase 0.4 0.4 0.4 Termamyl 0.30 0.6 0.6 Carezyme — 0.6 0.6 PEI1800 E7 AO 1.0 — — PEI 1200 E7 AO — 1.0 1.0 HEDP 0.2 — — BPT — — 0.2Glycolic — 0.2 0.2 Polycarboxylic — 0.2 0.2 Balance (Moisture andMiscellaneous) to 100

EXAMPLE 4

The following liquid detergent formulation, according to the presentinvention was prepared:

FF C25AS 13 C25E3S 2 TFAA 6 C12-14 alkyl dimethylhydroxy ethyl ammoniumchloride 1 Cationic ester 1.5 TPKFA 15 Citric acid 1 Ethanol 2 1,2Propanediol 8 NaOH up to pH 7.5 DTPMP 1.2 Savinase 0.5 Termamyl (300KNU/g) 0.15 Boric acid 1.5 Softening clay of the bentonite type 4Suspending clay SD3 0.3 PEI 1200 E7 1 HEDP 0.2 Balance (Moisture andMiscellaneous) 100

What is claimed is:
 1. A fabric care composition comprising a polyaminefunctional polymer having a molecular weight between 200 and 10,000, anda crystal growth inhibitor selected from the group consisting ofcarboxylic compounds, organic mono and diphosphonic acids, and salts andcomplexes thereof, and mixtures thereof, wherein, when said crystalgrowth inhibitor is selected from carboxylic acid, organic diphosphonicacid, and mixtures thereof, the crystal growth inhibitor is present inan amount of less than 1% by weight of the composition.
 2. A compositionaccording to claim 1, wherein said polymer comprises a polyaminebackbone corresponding to the formula:

having a polyamine formula V_((n+1))W_(m)Y_(n)Z or a polyamine backbonecorresponding to the formula:

having a polyamine formula V_((n−k+1))W_(m)Y_(n)Y′_(k)Z, wherein k isless than or equal to n, said polyamine backbone has a molecular weightgreater than 200 daltons, wherein i) V units are terminal units havingthe formula:

ii) W units are backbone units having the formula:

iii) Y units are branching units having the formula:

 and iv) Y′ units are branch point for a backbone or branch ring havingthe formula:

v) Z units are terminal units having the formula:

 wherein backbone linking R units are selected from the group consistingof C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂dihydroxy-alkylene, C₈-C₁₂ dialkylarylene, —(R¹O)_(x)R¹—,—(R¹O)_(x)R⁵(OR¹)_(x)—,—(CH₂CH(OR²)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH(OR²)CH₂)_(w)—,—C(O)(R⁴)_(r)C(O)—, —CH₂CH(OR²)CH₂—, and mixtures thereof; wherein R¹ isselected from the group consisting of C₂-C₆ alkylene and mixturesthereof; R² is selected from the group consisting of hydrogen,—(R¹O)_(x)B, and mixtures thereof; R⁴ is selected from the groupconsisting of C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene,C₆-C₁₀ arylene, and mixtures thereof; R⁵ is selected from the groupconsisting of C₁-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂dihydroxy-alkylene, C₈-C₁₂ dialkylarylene, —C(O)—, —C(O)NHR⁶NHC(O)—,—R¹(OR¹)—, —C(O)(R⁴)_(r)C(O)—, —CH₂CH(OH)CH₂—,—CH₂CH(OH)CH₂O(R¹O)_(y)R¹OCH₂CH(OH)CH₂—, and mixtures thereof; R⁶ isselected from the group consisting of C₂-C₁₂ alkylene or C₆-C₁₂ arylene;R′ units are selected from the group consisting of hydrogen, C₁-C₂₂alkyl, C₃-C₂₂ alkenyl, C₇-C₂₂ arylalkyl, C₂-C₂₂ hydroxyalkyl,—(CH₂)_(p)CO₂M, —(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M, —(CH₂)_(p)PO₃M,—(R¹O)_(x)B, —C(O)R³, and mixtures thereof; B is selected from the groupconsisting of hydrogen, C₁-C₆ alkyl, —(CH₂)_(q)SO₃M, —(CH₂)_(p)CO₂M,—(CH₂)_(q)(CHSO₃M)CH₂SO₃M, —(CH₂)_(q)—(CHSO₂M)CH₂SO₃M, —(CH₂)_(p)PO₃M,—PO₃M, and mixtures thereof; R³ is selected from the group consisting ofC₁-C₁₈ alkyl, C₇-C₁₂ arylalkyl, C₇-C₁₂ alkyl substituted aryl, C₆-C₁₂aryl, and mixtures thereof; M is hydrogen or a water soluble cation insufficient amount to satisfy charge balance; X is a water soluble anion;m has the value from 2 to 700; n has the value from 0 to 350; p has thevalue from 1 to 6, q has the value from 0 to 6; r has the value of 0 or1; w has the value 0 or 1; x has the value from 1 to 100; y has thevalue from 0 to 100; z has the value 0 or
 1. 3. A composition accordingto claim 2, wherein R′ units of the amino functional polymer areselected from the group consisting of hydrogen, C₃-C₂₂ hydroxyalkyl,benzyl, C₁-C₂₂ alkyl, —(R¹O)_(x)B, —C(O)R³, —(CH₂)_(p)CO₂ ⁻M⁺,—(CH2)_(q)SO₃ ⁻M⁺, —CH(CH₂CO₂M)CO₂M and mixtures thereof, preferably R′units are selected from the group consisting of hydrogen, C₁-C₂₂ alkyl,—(R¹O)_(x)B, —C(O)R³, and mixtures thereof.
 4. A composition accordingto claim 3, wherein x has a value lying in the range of from 1 to
 20. 5.A composition according to claim 4, wherein said polymer is present inan amount of from 0.01% to 50% active by weight.
 6. A compositionaccording to claim 5, wherein said polymer is present in an amount offrom 0.1% to 20% active by weight.
 7. A composition according to claim1, wherein said crystal growth inhibitor is selected from carboxyliccompounds, organic diphosphonic acids, and mixtures thereof.
 8. Acomposition according to claim 7, wherein said organic diphosphoniccompound is hydroxy-ethane 1,1 diphosphonic acid.
 9. A compositionaccording to claim 1, wherein said crystal growth inhibitor is presentin an amount of from 0.005% to 0.5% by weight of the composition.
 10. Acomposition according to claim 9, wherein said crystal growth inhibitoris present in an amount of from 0.1% to 0.2% by weight of thecomposition.
 11. A composition according to claim 1, wherein saidcomposition further comprises a fabric softener.
 12. A compositionaccording to claim 11, wherein said softener is a cationic fabricsoftener, selected from

or the formula:

wherein Q is a carbonyl unit having the formula:

each R unit is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,and mixtures thereof, preferably methyl or hydroxy alkyl; each R¹ unitis independently linear or branched C₁₁-C₂₂ alkyl, linear or branchedC₁₁-C₂₂ alkenyl, and mixtures thereof, R² is hydrogen, C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, and mixtures thereof; X is an anion which iscompatible with fabric softener; the index m is from 1 to 4; the index nis from 1 to
 4. 13. A composition according to claim 1, wherein saidcomposition further comprises a dye fixing agent.
 14. A compositionaccording to claim 1, wherein said composition is in liquid form.
 15. Amethod for stabilizing a composition comprising amino-functional polymerhaving a molecular weight between 200 and 10,000, which comprises thestep of contacting said composition with a crystal growth inhibitorselected from the group consisting of carboxylic compounds, organic monoand diphosphonic acids, and salts and complexes thereof, and mixturesthereof.
 16. A method for providing care to colored fabric whichcomprises the step of contacting the fabric with a composition accordingto claim
 1. 17. A composition according to claim 1, wherein the crystalgrowth inhibitor comprises an organic diphosphonic acid.
 18. Acomposition according to claim 1, wherein the polyamine functionalpolymer has a molecular weight between 200 and
 2000. 19. A fabric carecomposition comprising a polyamine functional polymer and from 0.005 to0.2 percent by weight of a crystal growth inhibitor selected from thegroup consisting of carboxylic compounds, organic mono and diphosphonicacids, and salts and complexes thereof, and mixtures thereof.
 20. Acomposition according to claim 19, wherein the polyamine functionalpolymer has a molecular weight between 200 and 10,000.
 21. A compositionaccording to claim 19, wherein the weight ratio of the crystal growthinhibitor to the polymer is from 0.005:1 to 0.1:1.